Ammonia activation using a heteroleptic stannylene and lithium stannylenoid formation facilitated by hemilabile iminophosphorane-based ligands

Abstract

Heteroleptic stannylenes, featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands, were synthesized straightforwardly through formal C–H activation. Subsequently, they were investigated for their ability to activate ammonia through N–H bond scission. By combining synthetic modifications of the ancillary ligand framework and computational analyses, detailed insights into the mechanism of NH₃ activation by these systems were obtained, highlighting an activation pathway at tin without a change in oxidation state. Additionally, an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials, providing access to a novel lithium stannylenoid.